FORMULA SHEET PHYSICAL CHEMISTRY II
Volume, area, circumference (circle or sphere with radius r)
Circumference circle 2πr; area circle πr2
Area sphere 4πr2 ; volume sphere 43 πr3
Differential calculus
Primitive Function Derivative (wrt x)
1 p+1
p+1 x xp p xp−1
1
− a cos(ax) sin(ax) a cos(ax)
1
a sin(ax) cos(ax) −a sin(ax)
x 1
2 + 2a cos(ax) sin(ax) cos2 (ax) −2a cos(ax) sin(ax)
1 ax
a e eax a eax
ax+b a
a ln(ax + b) − x ln(ax + b) ax+b
Standard normal distribution (Gaussian function)
x2
f (x) = σ√12π exp − 2σ 2 : σ 2 = hx2 i = variance; σ = standard deviation.
R∞ 1/2 R ∞ R∞ π 1/2
exp(−ax2 )dx = 12 πa 1 1
0
; 0 x exp(−ax2 )dx = 2a ; 0 x2 exp(−ax2 )dx = 4 a3
R∞ 3 R∞ 1/2
0
x exp(−ax2 )dx = 2a12 ; 0 x4 exp(−ax2 )dx = 38 aπ5
Logarithms
log x = ln x/ ln 10; ln x = log x/ log e = ln 10 × log x
Series
1 2 1 3
ez = exp(z) = 1 + z + 2! z + 3! z + ··· every z
1 2 1 3 1 4
ln(1 + z) = z − 2 z + 3 z − 4 z · · · |z| ≤ 1, z 6= −1
1 3 1 5 1 7
sin z = z − 3! z + 5! z − 7! z + ··· every z
1 2 1 4 1 6
cos z = 1 − 2! z + 4! z − 6! z + ··· every z
tan z = z + 13 z 3 + 15
2 5 17 7
z + 315 z + ··· every z
(1 + x)−1 = 1 − x + x2 − x3 + x4 − x5 + · · · |x| < 1
(1 − x)−1 = 1 + x + x2 + x3 + x4 + x5 + · · ·
p |x| < 1
(1 + x) = 1 + 21 x − 2·4
1 1·3
x2 + 2·4·6 x3 − · · · |x| < 1
Physical constants and units
speed of light c = 299 792 458 m·s−1 (exact) 1 bar = 1×105 Pa =1×105 N·m−2 (exact)
Planck constant h = 6.626 075 5×10−34 J·s 1 J = 1 kg·m2 ·s−2 = 1 N·m = 1 C·V
−34
Dirac constant h/2π h̄ = 1.054 572 66×10 J·s 1 A = 1 C·s−1
−19
charge electron e = 1.602 177 33×10 C 1 S = 1 A·V−1
−31
mass electron me = 9.109 389 7×10 kg
mass proton mp = 1.672 623 1×10−27 kg 1 Å= 1×10−10 m
= 1.007 276 470 u 1 Poise = 0.1 N·m−2 ·s
mp /me = 1 836.152 701
atomic mass unit u = 1.660 540 2×10−27 kg
Avogadro’s number NAv = 6.022 136 7×1023 mol−1
Boltzmann constant kB = 1.380 658×10−23 J·K−1 n 10−9 (nano)
−1 −1
gas constant kB NAv R = 8.314 510 J·K ·mol p 10−12 (pico)
−1
Faraday constant eNAv F = 96 485.309 C·mol f 10−15 (femto)
−11 2 −2
Gravitational constant G = 6.670×10 N·m ·kg G 109 (giga)
−12 −1 −2 2
Permittivity vacuum 0 = 8.854×10 N ·m ·C T 1012 (tera)
1
Thermodynamics and Equilibria
R process with pV-work only: dU = T dS − pdV .
First Law: ∆U = q + w; for a reversible
Second Law: ∆Stot ≥ 0; ∆Ssystem = dqTrev
P
H = U + pV A = U − TS G = H − TS G= nJ µJ
µJ = (∂G/∂nJ )p,T,nI = µ0J + RT ln aJ ≈ µ0J + RT ln pJ /p0
0
Q νJ
Ka = ( J aνJJ )eq = exp[ −∆rG pJ
Q
RT ]; Kp = J p0
eq
∆r H 0 0
Van ’t Hoff equation: d ln K
dT = d ln K
RT 2 , or: d(1/T ) = − ∆rRH
∂(G/T )
Gibbs-Helmholtz equation: ∂(1/T ) = H
Boltzmann weight and (Maxwell-)Boltzmann distributions of molecular velocities or speeds
p(Ei )
Boltzmann weight: p(Ej ) = exp(−(Ei − Ej )/kB T )
1/2
mv 2
Velocity distribution in 1-D: f (vx )dvx = 2πkmB T exp − 2kBxT dvx
3/2
mv 2
3-D speed distribution: F (v)dv = 4πv 2 2πkmB T exp − 2k BT
dv
Kinetic gas theory and collision theory
q
collision frequency: zAB = σAB v rel NVB = σAB 8kB T NB
πµ V
µ = reduced mass = mmAA+m mB
B
= 12 m if mA = mB = m.
collision cross section σAB = πd2 = π(rA + rB )2
1 kB T
mean free path (for pure gas): λ = vz = σ√ 2 p
q
NA NB 8kB T
collision density: ZAB = V V σ πµ
Transport and diffusion
collision flux: ZW = 14 c NV
dc d2 c
Fick’s First Law: J(particles)= −D dx ; Fick’s Second Law (diffusion equation): dc
dt = D dx2 .
Diffusion coefficient D = kB T /ff r = ukB T ; for ions D/kB T = u/ze.
Mobility u is drift speed s per unit applied force: s = uF .
u = 1/ff r ; ff r = friction coefficient; Stokes: ff r = 6πηa for sphere of hydrodynamic radius a.
Thermodynamic force Fth = − dµ dx (per mole)
Diffusion-limited reaction rate constant: kd = 4πR∗ DNAv
R∗ = reaction distance; D = sum of diffusion constants reactants.
Viscosity η: J(momentum)x = −η dv dz
x
−2 −1 −1
η = viscosity in N·s ·m = kg·m ·s
cgs unit g·cm−1 ·s−1 = 0.1 kg·m−1 ·s−1 is called Poise
Statistical Thermodynamics
P P
Canonical Partition Function: Q = i exp[−Ei /kB T ] = i exp[−βEi ]
U = i pi Ei = i Ei exp[−E i /kB T ]
P P P
Q ; Statistical Entropy: S = −kB i pi ln pi
A = −kB T ln Q
